JP3125242B2 - Solid fixing agent for processing silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent for a silver halide photographic material, and more particularly to a solid fixing agent for rapid processing of a silver halide photographic material.

[0002]

2. Description of the Related Art In general, a series of processes such as development and fixing of a black-and-white silver halide photographic light-sensitive material are carried out by sequentially moving a film exposed to each processing solution tank by an automatic developing machine using a transport roller. Development and fixing processing are performed.

In this case, the treating solution is prepared by dissolving a treating agent concentrate prepared in advance by a treating agent liquid dispenser (chemical mixer) in a fixed amount of water, and is supplied to each tank by a magnet pump via a conduit. The temperature is adjusted to ~ 40 ° C.

Accordingly, in order to prevent the reaction between the processing agents, the components of the processing solution are separated and handed to the user as a concentrated solution.
The processing solution can be prepared only by dilution. The X-ray developer is composed of three kinds of concentrated liquids: a kit containing a developing agent or an alkaline agent, a kit containing a developing agent, an auxiliary agent, an acid agent, and a kit containing a hardener.

[0005] The fixing solution is distributed in the form of a concentrated solution comprising a kit containing a fixing agent and a preservative and a kit containing a hardening agent. There are many problems such as soaring distribution costs due to the form.

[0006] In the case of a so-called powder processing agent obtained by solidifying the components of a photographic processing agent, the size and weight of the processing agent can be greatly reduced as compared with a liquid type processing agent, which is very advantageous for transportation and storage. For this reason, various improvements have been made and are still used today.

Although a thiosulfate is generally used as a fixing agent, it is preferable to increase the thiosulfate concentration in order to obtain a quick fixing property. However, if the thiosulfate concentration is increased, the water washability after fixing deteriorates, resulting in an increase in the amount of residual thiosulfate and adversely affecting the preservation of images, as well as causing environmental pollution due to the discharge of the wash water. Had the problem of

On the other hand, the present inventor studied ammonium thiosulfate having a high fixing ability as a solid fixing agent. Defects such as deterioration of stability were observed. In order to improve storage stability deterioration due to deliquescence, there is a problem that a preparation environment and a packaging environment in a low humidity or vacuum sealed state are required, resulting in a high capital investment and a high cost.

In addition, sodium thiosulfate and potassium thiosulfate were examined as alternatives to ammonium thiosulfate, but deliquescence was improved but fixing ability was deteriorated.

[0010] As described above, ammonium thiosulfate has a deliquescent property, which is a major drawback in terms of storage stability as a solid fixing agent, and it is desired to develop a solid fixing agent kit having no deliquescent, excellent fixability, and high formulation efficiency. Mareta.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a solid fixing agent for processing a silver halide photographic light-sensitive material which has no deliquescence, has excellent fixing ability and does not deteriorate photographic performance. It is.

[0012]

The above-mentioned problems have been solved by the present invention described below. That is, in a processing agent used for automatic developing machine processing of an exposed black-and-white silver halide photographic light-sensitive material, a fixing processing agent is at least one selected from lithium thiosulfate, sodium thiosulfate, and potassium thiosulfate and represented by the following general formula [1]. A solid fixing agent for processing a black-and-white silver halide photographic light-sensitive material, characterized in that the solid fixing agent contains a mesoionic compound represented by the formula and is configured as a solid processing agent kit.

[0013]

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[0014] (wherein, Q represents a nonmetallic atomic group necessary to form a heterocyclic ring of 5 or 6-membered, A ^- is O ^-, S ^- or N ^- -
Represents R. R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. Hereinafter, the present invention will be described in detail.

The 5- or 6-membered heterocyclic ring represented by Q in the general formula [1] includes imidazoles, pyrazoles, oxazoles, thiazoles, triazoles,
Examples include tetrazoles, thiadiazoles, and oxadiazoles.

R in the formula is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, Or an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

Examples of the heterocyclic group represented by Q or R include a nitro group, a halogen atom, a mercapto group, a cyano group, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, an alkynyl group, an aralkyl group and an alkoxy group. , Aryloxy, alkylthio, arylthio, heterocyclic oxy, heterocyclic thio, sulfonyl, carbamoyl, thiocarbamoyl, sulfamoyl, carbonamido, sulfonamido, acyloxy, sulfonyloxy, ureido Group, thioureido group, sulfamoyl group, acyl group, thioacyl group,
It may be substituted with a heterocyclic group, an oxycarbonyl group, an oxycarbonylamino group, an amino group, a hydroxy group, a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, or the like.

Further, the compound represented by the general formula [1] is
Salts (eg, acetate, nitrate, salicylate, hydrochloride, iodate, bromate) may be formed. In the general formula [1], A ⁻ is preferably S ⁻ .

The mesoionic compound preferably used in the present invention includes a compound represented by the following general formula [2].

[0020]

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In the formula, X represents N or C—R ₂ , Y represents O, S, N—R ₃ , and Z represents N, N—R ₄ , or C—R _5.
Represents R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are an alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, amino group, acylamino group, sulfonamide group, ureido group , A sulfamoylamino group, an acyl group, a thioacyl group, a carbamoyl group or a thiocarbamoyl group. However, R ₂ and R ₅ may be hydrogen atoms. R ₁ and R ₂ , R ₁ and R ₄ , R ₁
And R ₅ , R ₃ and R ₄ and R ₅ may form a ring. The compound represented by the general formula [2] will be described in detail.

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group,
Represents an aralkyl group, an aryl group, a heterocyclic group, or an amino group, and these groups described above may have a substituent.
Further, it may be an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an acyl group, a thioacyl group, a carbamoyl group, or a thiocarbamoyl group. However, R ₂ and R ₅ may be hydrogen atoms.

In the general formula [2], X is preferably N,
Represents CR ₂ , Y represents NR ₃ or S, O, and Z represents N
Or C—R ₅ , wherein R ₂ , R ₃ or R ₅ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group. Represent. Provided that R ₂ and R ₅
May be a hydrogen atom. R ₃ is preferably a substituted or unsubstituted amino group, a substituted or unsubstituted thioacyl group, or a substituted or unsubstituted thiocarbamoyl group.

Hereinafter, specific examples of the compound of the present invention are shown, but the compound of the present invention is not limited thereto.

[0025]

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[0026]

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[0027]

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[0028] The general formula [1] or a compound represented by [2] of the present invention, Journal of Heterocyclic Chemistry (J.Heterocyclic Chem.) 2, 105 ,
(1965), 5, 277 (1968) Journal of Organic Chemistry (J. Org. Chem.) 30 , 567 (1965), 32 , 224
5 (1967), Journal of Chemical Society (J. Chem. Soc) 80 , 1895 (1958), 57 , 899 (1935), 81 ,
2, 865 (1959), Chemical Communication (Chem. Co.)
mmum.) 1222, 1224 (1971), Tetrahedoron Lett. 2939 (1972), 5881 (1968), 1809
(1967), 1578 (1971), Japanese Patent Laid-Open No. 60-87322, Berichte der Deutsches Hemising Gesellschaft (Berichte der Deutschen C)
hemischen Gesellschaft) 3
8 4049 (1905), JP-A-60-12293
No. 6, JP-A-60-117240, Advances in Hetero Chemistry
cyclic Chemistry) 19 1 (1976), Journal of
It can be synthesized by the method described in Chemical Society Perkin Transaction 1 (J. Chem. Soc., Perkin Trans. 1) 627 (1974), journal, etc.

The mesoionic compound is disclosed as a fixing agent, for example, a 1,2,4-triazolium-3-thiolate compound in JP-A-57-150842. In addition, JP-A-4-1437
Nos. 55 and 4-143757, which are used alone as a desilvering agent, and further disclosed in JP-A-4-130431, JP-A-4-143756, JP-A-4-17
No. 0539 and No. 4-22860 disclose the use in combination with ammonium thiosulfate, but do not mention the solid fixing agent kit. In the present invention, the solid fixing agent has a granular shape. In order to form a granulated product, it is preferable to use a commonly used granulation aid, and water of crystallization of an additive is preferably used.
A small amount of water, water-soluble or alkali- or acid-soluble polymer is used. For example, gelatin, pectin, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone,
Vinyl acetate copolymer, polyethylene oxide,
Carboxymethylcellulose sodium, hydroxypropylcellulose, methylcellulose, ethylcellulose, alginic acid, chitanic acid gum, gum arabic, tragacanth gum, karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, polyoxyethylene ethyl ether, polyoxyethylene stearyl ether, etc. Polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers such as polyoxyethylene noctyl phenol ether and polyoxyethylene nonyl phenol ether, or water-soluble binders described in Japanese Patent Application No. 2-203165 by the same applicant as the present invention. It can be used in combination with at least one binder selected from among them.

The granulation method applied to the solid fixing agent of the present invention includes rolling granulation, extrusion granulation, compression granulation, and the like.
A crushing granulation method, a stirring granulation method, a spray drying method, a dissolution solidification method and the like can be used, and an extrusion granulation method and a compression granulation method are particularly preferable.

The particle size and shape of the granulated material suitable for the present invention vary depending on the desired properties, but generally the solubility desired for the photographic processing agent and the amount or transport of the residual powder in the waste packaging material after preparation. Considering the durability against breaking of granules due to vibration at the time, in the case of granular, the spherical equivalent particle size may be about 0.5 mm to 50 mm, preferably about 1 mm to 15 mm, and the shape may be cylindrical, spherical , A cube, a rectangular parallelepiped, etc., and more preferably a spherical or cylindrical shape.

In the case of a tablet, a diameter of about 2 mm to 5 cm is preferable, though it also depends on the desired properties. When it is desired to improve the solubility, a plate-shaped tablet having a reduced tablet thickness, a tablet having a further reduced central portion of the plate-shaped tablet, a hollow donut-shaped tablet, and the like are also useful. Conversely, the diameter may be further increased for the purpose of slow dissolution.

The surface state (smooth, porous, etc.) may be changed to control the solubility.

It is possible to give different solubilities to a plurality of granules,
It is also possible to take a plurality of shapes in order to match the solubility of materials having different solubility. In this case, the inner layer is a granulating agent such as a developing agent, a preservative, and a water-soluble polymer, and the outermost layer is a granulating agent such as an alkali agent, a development inhibitor, and a water-soluble polymer. The form of the agent is preferred.

The photographic processing agent used in the present invention is not particularly limited, and any known photographic processing agent can be applied.

As the fixing agent in the solid fixing agent of the present invention, sodium thiosulfate, lithium thiosulfate and potassium thiosulfate are preferable, and sodium thiosulfate is particularly preferable. In the present invention, the reason that ammonium thiosulfate is removed is that ammonium thiosulfate has a drawback that the solid fixing agent kit has a high deliquescence and lacks stability in a production process and a distribution process.

However, when sodium thiosulfate having a low deliquescent property is used, there is a problem that the fixing ability is lowered, and therefore a fixing accelerator is required.

However, fixing accelerators generally known in the art, for example, JP-A-45-35754 and JP-B-58
-122535, 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, US Patent 4,126,459
Even when thioether described in the above is used in combination with sodium thiosulfate, a satisfactory fixing promoting effect cannot be obtained by the current rapid processing.

When the mesoionic compound according to the present invention is combined with the above thiosulfate, a fixing solution having a high fixing speed can be obtained.

The concentration of the thiosulfate as the fixing solution is preferably 0.1 to 5 mol / l, more preferably 0.1 to 5 mol / l.
5 to 2 mol / l, more preferably 0.7 to 1.
8 mol / l.

The mesoionic compound used in the fixing solution of the present invention is preferably used in an amount of 0.003 to 1.0 mol / liter, more preferably 0.01 to 1.0 mol / l.
0.50.50 mol / l is particularly preferred.

The fixing agent contains a sulfite as a preservative,
The concentration of the sulfite is 0.2 mol / liter or less, and preferably 0.1 mol / liter or less, when the thiosulfate and the sulfite are dissolved and mixed in water. Sulfites include solid lithium, potassium, sodium,
An ammonium salt or the like is used, and is dissolved and used together with the solid thiosulfate. Further, the fixer preferably contains citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid, and optical isomers thereof, and the salts thereof include, for example, potassium citrate, lithium citrate, and sodium citrate. , Ammonium citrate, lithium bitartrate, potassium bitartrate, potassium tartrate, sodium bitartrate, sodium tartrate, ammonium bitartrate, ammonium potassium tartrate, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate Preferred examples thereof include lithium, potassium, sodium, and ammonium salts, and one or more of these can be used in combination.

Among the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof.

The citric acid, tartaric acid, malic acid, succinic acid and the like are supplied as solids, and are used after being dissolved in an aqueous solvent. The preferred content in the fixing solution after dissolution is 0.05 mol / l or more. The preferred content is 0.2 to
0.6 mol / liter. In the fixing solution, in addition to the above compounds, various acids, salts, chelating agents, surfactants, wetting agents,
And the above-mentioned fixing accelerator and the like.

Examples of the above-mentioned acids include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, formic acid, propionic acid,
Organic acids such as oxalic acid and malic acid are exemplified.

Examples of the salt include salts of these acids such as lithium, potassium, sodium and ammonium.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. And the like.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Among the above additives, acids and salts such as sulfuric acid, boric acid and aminopolycarboxylic acids are preferred. The preferred amount of the additive is 0.5 to 20 g / liter.

The solid developer used in the present invention includes:
As the developing agent, dihydroxybenzenes, 3-pyrazolidones, aminophenols, 1-allyl-3-aminopyrazolines, ascorbic acid, pyrazolones and the like, or a mixture thereof are used.

In addition, LFA Mason Photographic Proce
ssing Chemistry (Focal Press, 1966) 226-229
Page, JP-A-48-64933 and the like. If necessary, a preservative (eg, sulfite, bisulfite, etc.), a buffer (eg, carbonate, borate, borate, alkanolamine, etc.), an alkali agent (eg, carbonate, etc.) Auxiliaries (eg, polyethylene glycols and esters thereof), pH adjusters (eg, organic acids such as citric acid), sensitizers (eg, quaternary ammonium salts), development accelerators, hardeners (eg, glutar) Dialdehydes such as aldehydes), surfactants and the like. The developer further includes an azole-based organic antifoggant (for example, indazole-based, imidazole-based, benzimidazole-based, triazole-based, benztriazo-based, tetrazole-based, and thiadiazole-based) as a fog-preventing agent, and tap water used in a processing solution. There are sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, and the like, which are concealing agents for concealing calcium ions mixed in.

The solid fixing agent according to the present invention may be used for X ray, for printing plate making, for general black and white, for laser light source, for CRT photographing,
The present invention can be applied to various black-and-white silver halide photographic materials such as photographic materials for reproduction and II indirect use.

In the silver halide photographic material to which the processing agent according to the present invention can be applied, the silver halide emulsion is any silver halide such as silver iodobromide, silver iodochloride and silver iodochlorobromide. However, silver iodobromide is preferable in that high sensitivity can be obtained.

These emulsions can be prepared by using a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. Good.

The size of silver halide grains used in the emulsion is not limited, but is preferably 0.05 to 2 μm.
In the silver halide grains of the present invention, it is preferable that at least 40% by weight or the number of grains are substantially cubic or tetradecahedral grains, and the apex of the crystal surface is rounded.

The size distribution of the silver halide grains may be monodisperse or polydisperse, but monodisperse is preferred. Here, monodisperse is a dispersion system in which 95% of the particles fall within a size of ± 40% of the number average particle size. Although the internal structure of the silver halide grains used in the present invention is optional, those having a core / shell structure having different silver halide compositions are preferred.

The emulsion may be subjected to a washing method such as a noodle washing method or a flocculation sedimentation method to remove soluble salts. For example, aromatic emulsions containing a sulfo group described in JP-B-35-16086 may be used. A method using an aldehyde resin, or an aggregating polymer agent described in JP-A-2-7037, exemplified G
3, a method using G8 or the like is a particularly preferred desalting method.

In the silver halide emulsion, various photographic additives can be used before and after physical ripening or chemical ripening. For example, Research Disclosure No. 176
43 (December 1978), No. 18716 (November 1979) and N
o. 308119 (December 1989). The types and locations of the compounds shown in these three research disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 page classification page page classification chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 III desensitizing dye 23 IV 998 B dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right Fog inhibitor / stabilizer 24 IV 649 Upper right 1006 ~ 7 VI Brightener 24 V 998 V Surfactant 26 ~ 7 XI 650 Right 1005 ~ 6 XI Charge Inhibitor 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1009-4 XXII Support 28 XVII 1009 XVII Examples of the support that can be used include those described on page 28 of RD-17643 and page 1009 of RD-308119.

A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer.

[0062]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 Preparation of Film Sample Preparation of Seed Emulsion 1 An iodine containing 2 mol% of silver iodide having an average grain size of 0.3 μm by a double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0. Monodispersed cubic silver halide particles were prepared. The obtained reaction solution is
After desalting at 0 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas Co. and an aqueous solution of magnesium sulfate, an aqueous solution of gelatin was added and redispersed to obtain a seed emulsion. Growth from Seed Emulsion 1 Using the above seed emulsion, grains were grown as follows. First
The seed emulsion was dispersed in an aqueous gelatin solution maintained at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. An aqueous solution of ammonium nitrate ion and an aqueous solution of potassium bromide and potassium iodide were added to this solution by a double jet method. During the addition, the pAg was controlled to 7.3, the pH was controlled to 9.7, and a layer having a silver iodide content of 35 mol% was formed. Next, an aqueous solution of ammonium silver nitrate and an aqueous solution of potassium bromide were added by a double jet method. The pAg was maintained at 9.0 until 95% of the target particle size, and the pH was continuously changed from 9.0 to 8.0. Then, adjust pAg to 11.0 and p
While maintaining H at 8.0, it was grown to the target particle size. Subsequently, the pH was lowered to 6.0 with acetic acid, and 5,5′-dichloro-9-ethyl-3,3
Add anhydrous 400 mg / mol AgX of '-di- (3-sulfopropyl) oxacarbocyanine sodium salt (sensitizing dye, GD-1) and remove using an aqueous solution of Demol N manufactured by Kao Atlas Co. and an aqueous solution of magnesium sulfate. After salting, a gelatin solution was added to redisperse.

According to this method, a tetrahedral tetrahedron having an average silver iodide content of 2.0 mol with a rounded apex and an average grain size of 0.40 μm and 0.65 μm was used.
μm, 1.00 μm, coefficient of variation (δ / r) 0.17,
16, 0.16 monodispersed silver iodobromide emulsions (A), (B) and (C) were prepared.

Preparation of Seed Emulsion 2 Including hydrogen peroxide-treated gelatin stirred vigorously at 40 ° C.
An equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin is added to the 05N aqueous potassium bromide solution by the double jet method, and after 1.5 minutes to 30 minutes at 25 ° C.
After the temperature of the solution was lowered to 80 ml, an aqueous ammonia solution (28%) of 80 ml per mol of silver nitrate was added, and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalted using an aqueous solution of Demol-N and an aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., and redispersed by adding an aqueous solution of gelatin.

The obtained seed emulsion was spherical grains having an average particle size of 0.23 μm and a coefficient of variation of 0.28.

Growth from Seed Emulsion 2 Using the seed emulsion described above, grains were grown as follows. An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by double jet method to an aqueous solution containing ossein gelatin and propyloxy-polyethyleneoxydisuccinate disodium salt vigorously stirred at 75 ° C. PH =
5.8, pAg = 9.0. After completion of the addition, the pH was adjusted to 6.0, and 400 mg / mol AgX of sensitizing dye GD-1 was added. further
After desalting at 40 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas, an aqueous solution of gelatin was added and redispersed.

According to this method, a tabular silver iodobromide emulsion (D) having an average silver iodide content of 1.5 mol%, a projected area diameter of 0.96 μm, a coefficient of variation of 0.25, and an aspect ratio (projected area diameter / grain thickness) of 4.0 was obtained. Was prepared.

Preparation of Samples The emulsions (A), (B), (C) and (D) thus obtained were each subjected to the above-mentioned sensitizing dye GD-1 and 55,5′-di- (55 ° C.) at 55 ° C. (Butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt
(A) 975 mg, (B) 600 mg per mol of silver halide (sensitizing dye / GD-2) anhydride (200: 1 weight ratio)
390 mg of (C) and 500 mg of (D) were added.

After 10 minutes, chloroauric acid, sodium thiosulfate,
Ammonium thiocyanate was added for chemical ripening.
Fifteen minutes before the completion of ripening, 200 mg of potassium iodide was added per mole of silver halide, and then 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene in 3 × 1 per mole of silver halide
0 to ² mol was added and dispersed in an aqueous solution containing 70 g of gelatin. Of the four types of ripened emulsions, (A), (B) and (C) were mixed at a weight ratio of 15:65:20 to give emulsion-I, (D)
Was used alone as Emulsion-II.

To each of Emulsion-I and Emulsion-II, additives as shown in JP-A-2-301744, page 95, line 16 to page 96, line 20 were added.

Further, 1.2 g of a dye emulsified dispersion shown below was added to prepare an emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresyl phosphate and 85 liters of ethyl acetate.
This is called an oil-based solvent. On the other hand, a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) is called an aqueous solvent. Next, put the oil-based solvent and the water-based solvent into the dispersion kettle,
The dispersion was performed while maintaining the liquid temperature at 40 ° C.

[0075]

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The additives used for the protective layer are as follows. The amount of addition is indicated by the amount per liter of the coating solution.

Coating solution for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethyl methacrylate (matting agent having an area average particle size of 5.0 μm) 1.1 g Silicon dioxide particles (Mat agent having an area average particle size of 3.0 μm) 0.5 g Ludox AM (colloidal silica manufactured by DuPont) 30 g 40% aqueous solution of glyoxal (hardener) 1.5 ml CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 500 mg

[0078]

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The emulsion layer had a silver equivalent of 2.0 g per side.
/ m ^2, 2.1 g / m ² as a weight with a gelatin protective layer at a speed per minute 90m by two slide hopper type coater so that the 0.99 g / m ² as a weight with gelatin, glycidyl methacrylate - methyl acrylate Emulsion on a 175 μm polyethylene terephthalate base coated with an aqueous dispersion of a copolymer obtained by diluting a butyl methacrylate copolymer (50:10:40 wt%) to a concentration of 10 wt% as a subbing liquid The layer and the protective layer were simultaneously coated on both sides and dried in 2 minutes and 15 seconds to obtain a film sample.

(Preparation of a solid processing agent) 1. Preparation of a solid developer From the developer formulation shown below, components other than sodium carbonate as an alkaline agent, sodium sulfite as a preservative, and sodium metabisulfite were used. After adding gelatin corresponding to 5% by weight, the mixture was extruded to a particle size of 2.5 mm and granulated by a granulation method.

The obtained granules were put into a rotating drum (pan) of a vacuum drying type pan coating apparatus VG (manufactured by Kikusui Seisakusho Co., Ltd.), and a 10% polyvinyl alcohol solution was sprayed on the granules rotating in the pan. .

Similarly, a mixture of sodium carbonate, potassium sulfite, and potassium metabisulfite was added with 5% by weight of gelatin, extruded to a particle size of 2.5 mm, and sprayed with a 10% polyvinyl alcohol solution in the same manner.

The obtained two types of granules were combined and vacuum-packed by a conventional method to obtain a solid developer.

Developer formulation (formulation of 1 liter of working solution) 1,4-dihydroxybenzene 15.0 g 1-phenyl-3-pyrazolidone 0.5 g potassium bromide 9.0 g trisodium hydroxyethylethylenediaminetriacetate 1.0 g 5-methylbenzotriazole 0.160 g 4-methyl-1-phenyl 5-mercaptotetrazole 0.020 g 5-nitroindazole 0.150 g cyclodextrin 5.0 g sodium carbonate 66 g potassium sulfite 49.5 g potassium metabisulfite 3.0 g 2. Preparation of solid fixative Among them, 5% gelatin by weight was added to the constituent drugs except tartaric acid and aluminum sulfate, and 2.5m
It was granulated by an extrusion granulation method with a particle size of m. The obtained granules are put into a rotating drum (pan) of a vacuum drying type pan coating apparatus (identical to the above), and the granules tumbling in the pan are added to the granules.
% Polyvinyl alcohol solution was spray-coated. Next, 5% by weight of gelatin was added to a mixture of tartaric acid and aluminum sulfate, and granules obtained by extrusion granulation with a particle size of 2.5 mm were put into a rotating drum (pan) of a vacuum drying type pan coating apparatus. The granules tumbling in the pan were spray-coated with a 10% polyvinyl alcohol solution. These two types of granules were vacuum-packed by a conventional method to obtain a solid fixing agent.

Fixing agent formulation (formulation of 1 use solution) Thiosulfate Amount shown in Table 2 Compound of general formula [1] Amount shown in Table 2 Anhydrous sodium sulfite 8 g Sodium citrate 2 g Sodium oxalate 2 g Boric acid 5 g Ethylenediaminetetraacetic acid 2 Sodium 0.5 g Sorbitol 3 g Tartaric acid 5 g Aluminum sulfate 10-18 hydrochloride 6.7 g The following compound described in U.S. Pat.No. 4,276,374 is used as a fixing accelerator in the system of sodium thiosulfate according to the present invention and a compound of the general formula (I). A combined fixer was also prepared.

Fixing accelerator (a): NaO ₃ S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ Na (b): NaO ₃ S (CH ₂ ) ₃ S (CH ₂ CH ₂ ) ₂ S (CH ₂ ) ₃ SO ₃ Na 3. Evaluation method of solid processing agent <Evaluation of disintegration> The obtained solid developer and fixing agent are applied to a paper packaging material whose inner wall is coated with polyethylene. After filling with no gap and vibrating for 24 hours with a commercially available vibration tester, the amount of fine powder formed by disintegration was visually evaluated on a 5-point scale.

5 is a good level with almost no fine powder, and 3 or less is not practical because there is a lot of fine powder adhered to the packaging material, and when the packaging material is opened or a processing agent is added, fine powder is scattered. Represents

<Evaluation of water solubility> Similarly, 70 g of a granular sample of a developer and a fixing agent was dissolved in 1 liter of water at 30 ° C. while stirring, and the time until complete dissolution was measured to evaluate the solubility. And When the dissolution takes more than 5 minutes, the dissolution by hand and the workability with an automatic liquid preparation machine (chemical mixer) are poor and not practical. The results obtained are shown below, and it can be seen that the solid fixing agent according to the present invention has little disintegration and excellent water solubility.

[0089] 4. Evaluation of processability <Evaluation of photographic performance> The obtained sample film was used as a fluorescent intensifying screen.
Sandwiched by KO-250 (manufactured by Konica Corporation), tube voltage 90KVP, 20mA
Then, X-rays were irradiated for 0.05 seconds, and a sensitometric curve was created by a distance method to determine sensitivity and gamma. The sensitivity was determined as the reciprocal of the X-ray dose required to obtain a density of fog + 1.0, and expressed as a relative sensitivity when the sensitivity of sample No. 1 was set to 100. In addition, gamma was indicated by a gamma value of a straight line connecting densities of 1.0 to 2.0 in the characteristic curve.

The processing was carried out by using an automatic developing machine SRX-501 (manufactured by Konica Corporation), dissolving 1359 g of a solid developer in water and finishing to 16 liters. The solid fixing agent according to the present invention is 1840 g.
Was dissolved in water to make up to 10 liters. For dissolution, a chemical mixer was used as a treatment liquid.

The developing temperature was 35 ° C., the fixing temperature was 33 ° C., the washing water was at a temperature of 18 ° C., and 3.5 l / min were supplied. The processing conditions used for evaluating the samples are shown below.

Processing Step Step Processing temperature (° C) Processing time (seconds) Replenishment amount Insert-1.2 Development + migration 35 14.6 33 ml / quarter Fixing + migration 33 8.2 63 ml / quarter Rinse + migration 18 7.2 3.51 / min Squeeze 40 5.7 Drying 45 8.1 Total-45.0 Note that 4.5 g / l potassium bromide was added as a starter to the initial supply of the developing solution. <Evaluation of deliquescence> The obtained solid processing agent was 23 ° C and RH 55%.
Was left for 10 minutes under the conditions described above, and deliquescence was evaluated visually and by palpation in the following four ranks.

A: No change by visual inspection and palpation as before standing B: No change is observed by visual inspection, but slight stickiness by palpation C: Glitter is visually observed and sticky by palpation D: Visual inspection A drop of water is observed on the surface, and it is sticky to the extent that it adheres to the hand by palpation.

<Evaluation of Fixing Ability (Blank)>
Take the working solution of the solid fixing agent in a 100 ml beaker, immerse the film piece cut at 10 × 70 mm at 33 ° C,
The elution time of the coated emulsion was evaluated as the clearing time.

<Evaluation of Residual Hypo> A residual hypo detection solution (7 g of silver nitrate dissolved in 30 ml of glacial acetic acid and 1000 ml of pure water) was placed in five places on the treated test film.
It was added dropwise. After standing for 3 minutes, the solution was thoroughly wiped off using a filter paper, left for 15 hours at room temperature and normal humidity, and the resulting silver sulfide was analyzed using a photographic densitometer PDA-65 (manufactured by Konica Corporation) for spectral filtering.
Using a 436 ± 10 nm interference filter, the blue light transmission densities of the portion where the evaluation solution was dropped and the portion where the drop was not dropped were measured, and the difference was averaged to calculate the amount of residual hypo from a calibration curve obtained from a standard sample. The results obtained are shown in Tables 1 and 2 below.

[0096]

[Table 1]

[0097]

[Table 2]

As is clear from the table, the processing using the solid fixing agent containing the mesoionic compound represented by the general formula [1] of the present invention does not deteriorate the photographic characteristics such as sensitivity and gamma. It can be seen that the fixing agent is excellent in fixing performance (clearing time), and has good residual hypo and deliquescent properties. Further, it can be seen that the fixing agent of the present invention can obtain good processing properties even in the present invention or in a constitution composed of a plurality of types such as a fixing accelerator.

[0099]

According to the present invention, a solid fixing agent for a silver halide photographic light-sensitive material having no deliquescence, excellent fixing ability, and without deteriorating photographic performance was obtained. Further, the solid fixing agent of the present invention had little disintegration in a granular state and did not deteriorate in water solubility.

Claims (1)

(57) [Claims] 1. A processing agent used for automatic developing machine processing of an exposed black-and-white silver halide photographic light-sensitive material, wherein a fixing processing agent is at least one selected from lithium thiosulfate, sodium thiosulfate and potassium thiosulfate; A solid fixing agent for processing a black-and-white silver halide photographic material, comprising a mesoionic compound represented by the formula [1] and configured as a solid processing agent kit. Embedded image (Wherein, Q represents a group of non-metallic atoms necessary for forming a 5- or 6-membered heterocyclic ring, and A ⁻ represents O ⁻ , S ⁻ or N ⁻ —R. R
Represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. )